EP2236472A1 - Verfahren zum Aufbringen einer porösen Entspiegelungsschicht sowie Glas mit einer Entspiegelungsschicht - Google Patents

Verfahren zum Aufbringen einer porösen Entspiegelungsschicht sowie Glas mit einer Entspiegelungsschicht Download PDF

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Publication number
EP2236472A1
EP2236472A1 EP09014113A EP09014113A EP2236472A1 EP 2236472 A1 EP2236472 A1 EP 2236472A1 EP 09014113 A EP09014113 A EP 09014113A EP 09014113 A EP09014113 A EP 09014113A EP 2236472 A1 EP2236472 A1 EP 2236472A1
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Prior art keywords
antireflection coating
glass
particles
sol
applying
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EP09014113A
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German (de)
English (en)
French (fr)
Inventor
Inka Dr. Henze
Matthias Dr. Bockmeyer
Gabriele RÖMER-SCHEUERMANN
Hans-Joachim Schmitt
Harry Engelmann
Peter Zachmann
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Schott AG
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Schott AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
    • F24S80/50—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings
    • F24S80/52—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/478—Silica
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the invention relates to a method for applying a porous anti-reflection layer and a glass with an anti-reflection layer.
  • the invention relates to an anti-reflective glass for solar applications.
  • Coated glasses for solar applications are known.
  • porous antireflection coatings It is known, in particular, to apply porous antireflection coatings.
  • a method for applying porous anti-reflection layers is, for example, in the German Offenlegungsschrift DE 10 2005 007825 A1 described.
  • porous anti-reflection layers a mixture of the coating material and air, whereby the effective refractive index of the coating is reduced.
  • the US2007 / 0017567 A1 describes self-cleaning surfaces on solar modules, among others.
  • the photocatalytically active components are embedded in a matrix.
  • the layers have layer thicknesses of 200 nm. In these Areas are TiO 2 layers visually striking. Layers show a natural color from 20 nm (first yellow then red, blue and green) and from 5 nm reflection in the solar spectrum.
  • the effect of the photocatalytic materials is greatly limited by the integration into the matrix, so that only the particles protruding from the top of the layer exhibit activity.
  • the matrix components listed contain organic components that are degraded by photocatalysis. On the named litter layers (albedo surfaces), a chalking occurring in such cases may not be noticeable, but on solar modules, due to the chalking, scattering centers that reduce transmission occur.
  • the requirements for antireflective coatings for solar glass, especially for photovoltaic applications are high. So the glass should have a high transmission as possible in the entire range of visible light and in the near infrared range. The antireflection coating should therefore have the lowest possible refractive index.
  • the antireflective coating should be weather-resistant for decades. Also on the abrasion resistance of such antireflection coatings high demands are made.
  • glasses which have a titanium oxide-containing coating. Due to the photocatalytic effect of titanium oxide or titanium dioxide, a self-cleaning effect of the glass occurs. Such glasses are also referred to as self-cleaning glass.
  • the invention is based on the object to provide a method with which it is possible to provide a self-cleaning anti-reflection layer, which ensures a high transmission.
  • Another object of the invention is to provide an environmentally resistant, abrasion resistant, self-cleaning coating.
  • the object of the invention is already achieved by a method for applying a porous anti-reflection layer and by a glass for outdoor applications, in particular for architecture and solar applications, according to one of the independent claims.
  • Glass is defined in this invention than in essence transparent glass, glass ceramic or transparent, as a disk of suitable plastic material, such as soda-lime glass, Borofloat ®, solar glass and other, all of the glass ceramics, preferably, transparent glass-ceramics as Robax ®, Zerodur ® and more, as well as transparent optical plastics such as polymethyl methacrylate, cycloolefinic copolymers, polycarbonate and others.
  • suitable plastic material such as soda-lime glass, Borofloat ®, solar glass and other, all of the glass ceramics, preferably, transparent glass-ceramics as Robax ®, Zerodur ® and more, as well as transparent optical plastics such as polymethyl methacrylate, cycloolefinic copolymers, polycarbonate and others.
  • suitable plastic material such as soda-lime glass, Borofloat ®, solar glass and other, all of the glass ceramics, preferably, transparent glass-ceramics as Robax ®, Zerodur ® and more,
  • the invention relates to a method for applying a porous anti-reflection layer.
  • the anti-reflection layer is applied by means of a sol-gel process.
  • the titanium oxide does not cause a significant deterioration of the optical properties of a porous anti-reflection coating.
  • the layers according to the invention have a comparable refractive index as other porous antireflection layers, for example based on silica particles and silicon oxide matrix, and thus have very good antireflection properties with an additional photocatalytically active surface.
  • a titanium-containing precursor is used, and particles, in particular nanoparticles, for example nanoparticulate silicon oxide or silicon dioxide are added to the sol-gel solution.
  • the titanium-containing precursor leads to the formation of a titanium oxide-containing matrix.
  • the matrix resulting from hydrolysis and condensation after thermal treatment consists predominantly of amorphous titanium oxide having a residual organic content of 10-50%.
  • the residual organics are removed by a thermal treatment and a matrix of crystalline or partially crystalline TiO 2 is formed , preferably in the anatase modification.
  • the crystallite size of the nanoscale crystalline or partially crystalline TiO 2 is preferably between 4 and 35 nm, more preferably between 8 and 25 nm.
  • In the matrix are embedded nanoparticles, in particular silicon oxide-containing nanoparticles.
  • the matrix-forming titanium oxide preferably has a micro or mesoporosity of 1 to 25%.
  • the synthesis guide according to the invention is achieved in that the matrix-forming TiO 2 has formed only between and / or on the SiO 2 particles. This ensures that the accessible surface of photocatalytically active TiO 2 is large, while at the same time having a low mass fraction or volume fraction of TiO 2 in the layer. This ensures that despite the high refractive index of TiO 2, the refractive index of the amorphous-crystalline layer composite is low.
  • an antireflection coating having a refractive index of less than 1.38, preferably less than 1.34, and more preferably less than 1.30.
  • the anti-reflection layer is preferably formed as a single-layer anti-reflection layer, which, in contrast to alternating-layer systems, due to their Refractive index has an anti-reflection effect and at no wavelength increases the reflection of the composite material.
  • the antireflection coating is designed as a broadband antireflection coating.
  • the particles in particular the nanoparticles, have a refractive index of less than or equal to 1.7, preferably less than or equal to 1.6 and particularly preferably less than or equal to 1.55.
  • a glass provided with an antireflective coating according to the invention has a high transmission.
  • titanium oxide in the entire layer in particular of less than 40, preferably less than 20 and particularly preferably less than 15% by weight, is sufficient for a sufficient self-cleaning effect.
  • a sol-gel solution is used in which the ratio of particles to precursor is between 0.1 and 0.9, preferably 0.7 and 0.8, the ratio being calculated on a weight% basis.
  • the invention provides a glass in which the added particles at least 60, preferably at least 70 and more preferably at least 80% by weight of the finished antireflection coating occupy.
  • the invention provides a glass in which a porosity (open porosity) of between 20 and 40% by volume is present in the antireflection coating according to the invention.
  • a porosity open porosity
  • the pores are filled with air, the desired refractive index is achieved.
  • the particles are preferably formed from glass, glass ceramic or ceramic. With such nanoparticles, a high transparency of the layer can be achieved.
  • nanoscale particles preferably SiO 2 particles
  • the precursor may comprise, for example, a titanium halide, a titanium nitrate, a titanium sulfate and / or a tetraalkyl titanate (titanium tetraalkoxide).
  • titanium tetraalkyl titanate titanium tetraalkoxide
  • Titantetraethylat and titanium tetrapropylate provided as a precursor.
  • a hydrolysis-stabilized titanium-containing precursor is used in a preferred embodiment of the invention.
  • the titanium precursor is first reacted with a complex ligand.
  • complex ligands e.g. Ethyl acetoacetate, 2,4-pentanedione (acetylacetone), 3,5-heptanedione, 4,6-nonanedione or 3-methyl-2,4-pentanedione (2-methylacetylacetone), triethanolamine, diethanolamine, ethanolamine, 1.3
  • Propanediol, 1,5-pentanediol, carboxylic acids such as acetic acid, propionic acid, ethoxyacetic acid, methoxyacetic acid, polyethercarboxylic acids (eg, ethoxyethoxyacetic acid), citric acid, lactic acid, methylacrylic acid, acrylic acid.
  • the molar ratio of complexing ligand to titanium precursor is preferably 5 to 0.1, more preferably 2 to 0.6, particularly preferably 1.2 to 0.8.
  • the particles are not limited in their particle size distribution.
  • particle mixtures of different sizes are used in a preferred embodiment. Particularly preferred are mixtures in which a smaller particle distribution fills the gaps of a larger one.
  • the antireflection coating has micropores or mesopores, in particular open pores having an average pore diameter of 1 to 12 nm, preferably 3 to 8 nm.
  • the pore diameter can be determined, for example, by the method of ellipsometric porosimetry known to those skilled in the art. wherein H 2 O is used as sorbent. In this method, the change in the refractive index of a layer is determined as a function of the relative humidity.
  • the pores are stochastic bottleneck spores. In a particular embodiment, it may instead be pores having a rod-shaped geometry.
  • the titanium-containing precursor comprises a hydrolysis-stabilized, water-soluble, amorphous titanium complex of the titanium halides, titanium nitrates, titanium sulfates and / or tetraalkyl titanate, in particular titanium tetraethylate and titanium propylate.
  • targeted hydrolysis can still be carried out in order to achieve a better hydrolytic stability of the titanium precursor.
  • the particles are inorganic materials that are amorphous or crystalline or partially crystalline.
  • the particles are not limited in their shape, they may, for example, round, platelet-shaped, cylindrical, fibrous, angular, cubic and have other conceivable forms.
  • the molar ratio of water to titanium precursor is 10 to 0.1, preferably 7 to 3, more preferably 6 to 4.
  • the hydrolysis can be carried out under acidic conditions.
  • mineral acids such as HNO 3 , HCl, H 2 SO 4 or organic acids such as ethoxyacetic acid, methoxyacetic acid, polyethercarboxylic acids (eg ethoxyethoxyacetic acid), citric acid, paratoluenesulphonic acid, lactic acid, methylacrylic acid, acrylic acid are preferably added to the hydrolysis water.
  • the solvent of the reaction mixture is removed under reduced pressure.
  • a hydrolysis-stable, redispersible in polar (H 2 O, ethanol, n-propanol) and apolar (toluene) solvents precursor powder is obtained.
  • Another way to remove the solvent to recover a redissoluble titanium oxide precursor powder is to spray-dry the reaction mixture.
  • the amorphous water-soluble precursor powders used may contain dopants in an amount of ⁇ 10 mol%, based on transition metal oxides.
  • the doping may take place before or after the reaction of the titanium alcoholate with the polar complexing and chelating compound can be added.
  • suitable dopants are Fe, Mo, Ru, Os, Re, V, Rh, Nd, Pd, Pt, Sn, W, Sb, Ag and Co. These can be in the form of their salts, the synthesis approach or the medium in a corresponding stoichiometry be added.
  • the sol-gel solution is applied by a dipping method or by roll coating.
  • all other usual for liquid coatings application method can be used, such as spin coating, spraying, slot casting, flooding and brushing.
  • the dipping method is particularly suitable for a uniform double-sided coating of large glass substrates.
  • the roll coating method has the advantage over the dipping method that a coating in a system can be made inline on one or both sides and no large basins have to be provided.
  • the coating is very fast in this case, so that high throughputs are possible.
  • the antireflection coating is baked or sintered at a temperature between 300 and 1000 ° C., preferably between 450 and 700 ° C., particularly preferably between 500 and 700 ° C.
  • organic constituents which have formed from the sol are largely removed.
  • the layer obtained predominantly contains particles, for example silicon oxide particles, which are embedded in a matrix which consists at least partly of crystalline titanium oxide.
  • the step of burn-in may take place during a tempering process or a burn-in directly preceding the tempering process.
  • the particles are preferably added as a suspension of the sol-gel coating solution.
  • SiO 2 particles are produced by the Stöber process.
  • the particles can be both dense, microporous or mesoporous.
  • the morphology of the particles can be both spherical and irregular.
  • the coating solution it is also possible to add aluminum in the form of alkoxides, aluminum salts, complexes of the alkoxides with ethyl acetate or AlOOH.
  • complex ligands e.g.
  • Propanediol, 1,5-pentanediol, carboxylic acids such as acetic acid, propionic acid, ethoxyacetic acid, methoxyacetic acid, polyethercarboxylic acids (eg ethoxyethoxyacetic acid) citric acid, lactic acid, methyl acrylic acid, acrylic acid used.
  • further semimetal or metal oxides such as, for example, boron oxide, zirconium oxide, cerium oxide, and zinc compounds can be part of the titanium-containing matrix.
  • the combination of the nanoparticulate component with the matrix-forming titanium precursor takes place in an acid medium, in particular at a pH below 3, preferably below 2.5, and particularly preferably below 1.5.
  • a corrosion protection layer is applied between the substrate and the antireflection coating to reduce or prevent the corrosion of the glass, that is to say a layer which prevents the direct contact of water or H + ions with alkalis of the substrate glass.
  • a substrate in particular a glass substrate, therefore, first a first layer is applied, on which then the anti-reflection layer is applied.
  • the inventors have found that such glass corrosion processes can be effectively prevented by an intermediate layer which either prevents water from contacting the substrate glass or prevents alkali ions, especially sodium ions, from diffusing from the glass into the anti-reflection layer.
  • the anticorrosion layer makes it possible to combine a self-cleaning layer based on the photocatalytic effect of TiO 2 on soda-lime glass.
  • the corrosion protection layer can be applied, for example, as a dense silicon oxide layer.
  • the corrosion protection layer can be applied by flame pyrolysis or deposited by means of a PVD or CVD method.
  • the use of a dense sol-gel layer has been found to be useful. Particularly advantageous in this case is the use of a dense silicon-titanium-oxide mixed layer which has approximately the same refractive index as the substrate glass. It can be made thick, for example, without disturbing the optical properties of the overlying anti-reflection layer. The corrosion protection and barrier effect is therefore particularly pronounced in this case.
  • Another possibility for providing a corrosion protection layer is the leaching of the substrate glass, for example by means of a plasma treatment, can be removed by means of the alkali and / or alkaline earth components in the surface region with a relatively good selectivity.
  • a good corrosion protection effect is given in the context of the invention if the diffusion of alkalis according to the DIN test 52296 or of water is reduced by at least 30%, preferably by 50%, particularly preferably 75%.
  • the invention further relates to a glass, in particular for outdoor use, in particular a glass for solar applications.
  • the glass is preferably produced by a method according to the invention, comprises a glass substrate and a titanium-oxide-containing porous antireflection coating layer deposited on the glass substrate by means of a sol-gel process.
  • the glass comprises a layer in which particles, in particular nanoparticles, for example silicon oxide particles, are embedded in a matrix which comprises titanium oxide formed by a sol-gel process, in particular consisting essentially of titanium oxide.
  • the antireflection coating preferably comprises silicon oxide particles having a size between 1 and 100 nm, preferably 3 and 70 nanometers, particularly preferably in the range of 6 to 30 nanometers.
  • the particles preferably comprise at least 50, particularly preferably at least 70% by weight of silicon oxide. With particles that consist predominantly of silicon oxide, low refractive index can be achieved. Furthermore, silicon oxide is particularly resistant to chemical attack and environmental influences.
  • the glass substrate used is preferably an alkali glass, in particular a soda-lime glass. Such glasses are inexpensive and have a high transparency. In a particular embodiment, low-iron, UV-absorbing solar glass is used.
  • the glass according to the invention is particularly suitable in outdoor applications as part of a housing for a solar module, a solar receiver or as an auxiliary pane and as architectural glazing.
  • the layers according to the invention show a self-cleaning effect under UV radiation. This self-cleaning effect is due to the photocatalytic activity of TiO 2 in the anatase modification.
  • the photocatalytic activity of the TiO 2 is detectable even under the irradiation of light in the visible wavelength range of the light.
  • the anti-reflection layer is applied to a glass tube which is part of a photovoltaic module, in particular part of a CIGS-based photovoltaic module.
  • the antireflection coating preferably also has self-cleaning properties.
  • the structure of such a photovoltaic module is designed, for example, from inside to outside as follows: In the center, there is a refractive index-adapted solution or oil (immersion solution or oil) oil), followed by the inner tube of glass, which preferably consists of soda-lime glass or other sodium-containing glasses.
  • the thermal expansion of the inner tube is adapted to that of the absorber layer, in this case a CIGS layer, of the solar layer system and is between 7.5 * 10 -6 K -1 and 11 * 10 -6 K -1 , preferably between 8, 5 * 10 -6 K -1 and 10 * 10 -6 K -1 .
  • the solar layer system can be constructed from the inside to the outside as follows: inner tube / barrier (SiN; optional) / molybdenum / absorber layer (CIGS) / buffer layer (CdS) / window layer (ZnO).
  • the entire layer structure is in a preferred embodiment between 3 and 4 microns thick.
  • the outermost layer is separated by the above-described immersion solution or oil from a polymer tube, preferably acrylate tube due to the high transmission, which in turn is separated from the outer tube by the immersion solution or oil.
  • the outer tube is made of glass and should preferably have a similar thermal expansion coefficient as the inner tube. However, any glass which has a sufficiently high transmission is conceivable; preference is given to soda lime, aluminosilicate and borofloat glasses.
  • the outside of the glass tube is provided with the self-cleaning antireflection coating.
  • a corrosion barrier layer is applied, in particular deposited, under the self-cleaning antireflection layer.
  • the self-cleaning anti-reflection layer is applied to a planar CIGS photovoltaic module.
  • the preferably self-cleaning anti-reflection layer can be used on any solar application and is not limited in solar absorber layers and systems.
  • the glass according to the invention in particular for solar applications, preferably comprises a flat glass substrate or a tubular substrate and a titanium-dioxide-containing porous antireflection coating layer deposited by means of a sol-gel process.
  • the invention is not limited to the shape of the glass substrate to be coated, so that arbitrarily shaped glass substrates can be coated.
  • Amorphous hydrolysis-stabilized titanium oxide precursors were prepared according to the following syntheses:
  • 1.0 mol of titanium (IV) -ethylate solution are added dropwise with stirring 1.0 mol of acetylacetone within about 25 minutes, with a significant warming begins.
  • the lemon yellow solution is stirred for 45 min at room temperature and then hydrolyzed with 5 mol of water.
  • the solvent and other volatiles are removed in vacuo at 80 ° C and 40 mbar.
  • the powder is then dried for 4 hours at 125 ° C. A fine yellow precursor powder having an oxide content of about 56% by weight is obtained.
  • 1.0 mol of titanium (IV) propylate solution are added dropwise with stirring 1.2 mol ethoxyacetic acid within about 25 minutes, with significant warming began.
  • the lemon yellow solution is stirred for 45 min at room temperature and then hydrolyzed with 5 mol of water.
  • the solvent and other volatiles are removed in vacuo at 80 ° C and 40 mbar. This gives a gel with an oxide content of about 50 wt .-%.
  • Fig. 1 1 schematically shows a glass 1 which comprises a substrate glass 3 and a titanium oxide-containing antireflection coating 2 applied by means of a sol-gel process.
  • the anti-reflection layer 2 in this embodiment has a proportion of titanium dioxide between 5 and 20% and is therefore self-cleaning due to the photocatalytic action of titanium oxide.
  • the refractive index is less than 1.34.
  • a flame-resistant dense corrosion protection layer 4 is arranged in this exemplary embodiment, which prevents water in the porous antireflection coating 2 from coming into contact with the substrate glass 3 and thus causing glass corrosion in the substrate glass 3.
  • Fig. 2 schematically shows a detailed view of an anti-reflection layer 2.
  • the anti-reflection layer 2 comprises a formed by a sol-gel process matrix 5 of titanium dioxide, in which particulate silica 6 is embedded.
  • the antireflection coating can be prepared, for example, as follows:
  • acetylacetonate is added dropwise to 0.1 mol of titanium (IV) butylate solution while stirring. After the subsequent dropwise addition of 0.3 mol of H 2 O, the solution is stirred (1 h) and 10 g of 1,5-pentanediol added.
  • mechanically resistant antireflection layers can be produced at a drawing speed of 10-30 cm / min via the dip coating method, at a relative humidity of ⁇ 40% and a penetration temperature of 450-700 ° C.
  • the anti-reflection layer can be produced as follows:
  • acetylacetonate is added dropwise to 0.1 mol of titanium (IV) butylate solution while stirring. After the subsequent dropwise addition of 0.3 mol of H 2 O, the solution is stirred (1 h) and 10 g of 1,5-pentanediol added.
  • 480 g of a 15 wt .-% alcoholic dispersion of SiO 2 nanoparticles is added in isopropanol followed by stirring.
  • the particles used have an elongated, fibrous geometry with a mean diameter of 10-15 nm and a length of 30-150 nm. Subsequently, the solution is diluted with 2160 g of ethanol.
  • solution thus prepared can be prepared at a tensile rate of 10-30 cm / min via the dip coating process, at a relative humidity ⁇ 40% and a firing temperature of 450 - 700 ° C according to the invention layers.
  • a weather-resistant, self-cleaning glass could be provided, which is particularly suitable for solar applications.

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EP09014113A 2008-11-11 2009-11-11 Verfahren zum Aufbringen einer porösen Entspiegelungsschicht sowie Glas mit einer Entspiegelungsschicht Withdrawn EP2236472A1 (de)

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WO2011021383A1 (ja) 2009-08-17 2011-02-24 日本板硝子株式会社 光触媒膜を備えたガラス物品
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WO2012008427A1 (ja) * 2010-07-12 2012-01-19 セントラル硝子株式会社 低反射膜およびその形成方法およびそれを用いた低反射部材、並びに、低反射膜形成用塗布液およびその調製方法およびそれを用いた低反射部材
US9272947B2 (en) * 2011-05-02 2016-03-01 Corning Incorporated Glass article having antireflective layer and method of making
FR2974800B1 (fr) * 2011-05-05 2013-04-26 Saint Gobain Substrat transparent revetu d'un empilement de couches minerales dont une poreuse recouverte
EP2559670A1 (de) 2011-08-17 2013-02-20 CENTROSOLAR Glas GmbH & Co. KG Glas mit Korrosions-Schutzschicht und Verfahren zur Herstellung des Glases
CN103311320B (zh) * 2012-03-14 2016-12-14 江苏新源动力有限公司 太阳能电池用透明导电薄膜及其制备方法
US8883252B2 (en) * 2012-06-28 2014-11-11 Intermolecular, Inc. Antireflective coatings with self-cleaning, moisture resistance and antimicrobial properties
KR101372461B1 (ko) * 2012-07-26 2014-03-12 성균관대학교산학협력단 반사방지막, 이의 제조 방법 및 이를 이용한 태양전지
KR102243475B1 (ko) 2012-11-30 2021-04-23 코닝 인코포레이티드 반사 감소된 유리 물품 및 이를 제조하는 방법 및 용도
WO2014131441A1 (en) * 2013-02-27 2014-09-04 Siemens Aktiengesellschaft Glass tube with an antireflective layer with a composite material, method for manufacturing the glass tube, heat receiver tube with the glass tube and solar collector with the heat receiver tube
US9423532B2 (en) * 2013-03-12 2016-08-23 Intermolecular, Inc. Anti-reflection coatings with aqueous particle dispersions and methods for forming the same
EP2947179A1 (en) * 2014-05-21 2015-11-25 Areva Renouvelables Method of fabricating a coated substrate
CN108410221A (zh) * 2018-04-23 2018-08-17 刘峰 自清洁的涂层
US11772086B2 (en) * 2019-05-13 2023-10-03 GM Global Technology Operations LLC Multifunctional self-cleaning surface layer and methods of forming the same
CN113113497B (zh) * 2021-04-13 2023-01-24 河南大学 一种使用有机增效剂的太阳能电池及其制备方法
DE102022204392A1 (de) 2022-05-04 2023-11-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Selbstheilungsfähiger Glaswerkstoff, Verfahren zu seiner Herstellung und Verwendung

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